EP2231521B1 - Verfahren zur herstellung von mesoporösen materialien - Google Patents
Verfahren zur herstellung von mesoporösen materialien Download PDFInfo
- Publication number
- EP2231521B1 EP2231521B1 EP08863489.4A EP08863489A EP2231521B1 EP 2231521 B1 EP2231521 B1 EP 2231521B1 EP 08863489 A EP08863489 A EP 08863489A EP 2231521 B1 EP2231521 B1 EP 2231521B1
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- Prior art keywords
- structuring
- parts
- mesoporous
- structuring agent
- materials
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/02—Crystalline silica-polymorphs, e.g. silicalites dealuminated aluminosilicate zeolites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/033—Using Hydrolysis
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
Definitions
- the present invention relates to the field of porous materials, in particular mesoporous, their use, especially in the field of molecular sieves or catalysis, particularly in the field of petrochemistry, and reagents for preparing these materials.
- Inorganic porous materials are widely used, especially as catalysts or catalyst supports in many industrial applications. These materials have a large specific surface area and may have an amorphous, para-crystalline or crystalline structure. Amorphous materials, such as silica gel or alumina, do not have a long-range crystallographic order, whereas para-crystalline solids such as gamma or eta alumina are semi-ordered, thus showing ray diffraction peaks. X wide. These two classes of materials generally have a broad pore distribution, mostly in the size range from 1 to 100 nm, and more precisely in the range of mesopores, from 2 to 50 nm.
- M41S mesoporous silica materials having a uniform and adjustable pore size in the range of 1.3 to 10 nm were discovered.
- MCM-41 hexagonal
- MCM-48 cubic
- layered morphologies have been described.
- M41S materials are generated around assemblies of molecules.
- the first structures were obtained using micelles of surfactant molecules having an alkyl chain and a cationic polar head. These materials had a limited wall thickness, ranging from 0.8 to 1.2 nm, and low thermal stability.
- the structuring agent can become trapped inside the pores.
- the material is generally calcined at high temperature, which breaks down the structuring agent into smaller components that can be removed from the pores. Calcination can have negative effects, such as deterioration of the structure of the material, release of effluents that can cause environmental problems or high energy consumption.
- the present invention relates to a method of manufacturing mesoporous material, comprising the steps defined in claim 1.
- the structuring agent comprises identical structuring parts.
- the structuring agent comprises different structuring parts, and in particular two, three, four or even five different types.
- the structuring parts are hydrophilic polymers, soluble in water.
- the hydrophilic polymers used are hydrophilic double block copolymers, double hydrophilic graft copolymers, triblock copolymers, comb polymers, graft polymers, random copolymers, terpolymers and homopolymers.
- the non-reactive water-soluble component can be neutral (uncharged).
- it may be a polymeric segment of poly (ethylene oxide) type.
- the reactive component which can become insoluble in water under the effect of the addition of an inductor and / or under the effect of the variation of a physicochemical parameter, can be neutral or charged, negatively or positively.
- the component made insoluble can be made soluble again or reversibly, and either by the variation of the same parameter, or by another means, as another physicochemical parameter.
- water-soluble is intended to mean solubility in water at room temperature, this may be greater than or equal to 3 mg / ml, in particular greater than or equal to 6 mg / ml. and in particular greater than or equal to 8 mg / ml.
- insoluble in water is meant for the purpose of the present invention a solubility at room temperature in water and under the conditions making the insoluble component, in particular a solubility of less than or equal to 8 mg / ml, especially lower or equal to 6 mg / ml, and in particular less than or equal to 3 mg / ml.
- polymer is intended to mean a body composed of at least one repeating unit, in particular at least ten times, in particular at least twenty times, indeed at least fifty times, and especially at least a hundred times .
- the structuring parts are linked by at least one type of interaction, in particular chosen from hydrogen bonds, electrostatic bonds, coordination bonds, dipolar bonds, solvation and hydrophobic interactions.
- the process may make it possible to recover at least 70%, especially at least 75%, in particular at least 80%, even 85%, more particularly 90% and even more particularly at least 95% by weight of the two structuring parts.
- the solution comprising the two structuring parts recovered from a previous synthesis can in particular be reused as such for a new synthesis.
- the structuring agent may be in the form of colloids, and in particular colloids whose size and / or average diameter ranges from 1 nm to 10 micrometers, in particular from 1 nm to 2 micrometers.
- colloids in the sense of the present invention, particles whose size is greater than the molecules that constitute them (supramolecular size) but small enough for the mixture remains homogeneous. In particular, their size ranges from one nanometer (10 -9 m) to ten micrometers (or 10 -5 m). Colloids can still be called micelles or micellar aggregates.
- the formation of the structuring agent by the structuring parts may in particular be induced by addition of at least one inductor, the inductor may be a chemical component and / or a physical component.
- the inductor may allow the modification of at least one physico-chemical parameter, in particular "chemical” as the variation of the pH, of the ionic strength and / or "physical” as the modification of the temperature.
- the inductor may be an ion, such as protons or hydroxide ions during the pH change, a charged or neutral molecule, a charged or neutral polymer, a copolymer, block copolymer or random, grafted or combed.
- an ion such as protons or hydroxide ions during the pH change, a charged or neutral molecule, a charged or neutral polymer, a copolymer, block copolymer or random, grafted or combed.
- the inductor may be of opposite charge to the reactive component of the structuring part.
- a complexation between the inductor and the reactive component of the structuring part may make it possible to obtain colloids.
- they are structuring agents of the materials.
- thermosensitive component of the structuring part may be poly (N-isopropylacrylamide) (PNIPAAm) or Poly (vinyl ether) s.
- the structuring agent is formed in solution, in particular in aqueous solution.
- the process is carried out at low temperature, that is to say at a temperature of less than or equal to 200 ° C., especially at a temperature below 100 ° C., and in particular at room temperature.
- the method can make it possible to obtain the material at autogenous pressures of solutions, in particular aqueous solutions, brought to 200 ° C., but in general the process is carried out at atmospheric pressure.
- the subject of the invention is the use of at least one compound having at least two structuring parts assembled by at least one type of non-covalent reversible interaction as a structuring agent that can be recycled in the preparation of a porous material, especially at room temperature.
- the mesoporous material is formed from precursors of silica, alumina, silica-alumina, zirconia, titanium, such as, for example, silicon tetraethoxide (TEOS), aluminum alkoxides, alkoxides or lithium salts. titanium or zirconium.
- TEOS silicon tetraethoxide
- the material can also be formed from preformed mineral nanoparticles.
- the method uses the structuring parts and the precursor of the mesoporous material in a weight ratio (structuring part / total mass of the precursor material) ranging from 0.20 to 0.65, especially from 0.30 to 0.55. .
- this method can also make it possible to create mesoporosities in zeolites and / or zeotypes. This would create an intra-crystalline secondary porosity of structured mesopores existing at the micropores of the zeolite
- Known methods for obtaining materials comprising both micropores and mesopores may require high temperature heating which may cause defects in the material structure and / or asymmetric pores.
- the process according to the invention can make it possible to create mesoporosity without affecting the initial microporosity, in terms of composition and / or in terms of structure.
- the figure 1 describes a particular embodiment of the process in which the structuring agent, hydrophilic polymer, is formed by assembly, micellization in water, structuring parts, the assembly being induced in particular by modifying a parameter physico-chemical (step a), then the mesoporous material is formed, by inorganic polycondensation (step b), the structuring agent is then disassembled and released by an inverse modification to that of step a) a physical parameter- chemical (step c) and the structuring parts are recovered and can be reused.
- step a modifying a parameter physico-chemical
- step b inorganic polycondensation
- step c physical parameter- chemical
- the Figures 2 and 3 are nitrogen adsorption-desorption isotherms performed to characterize porous materials.
- the gas used to perform these measurements is nitrogen.
- These figures show on the abscissa the partial pressure (P / Po) in nitrogen and on the ordinate the adsorbed volume (in cm 3 / g) in the material.
- the figure 4 is an IR spectrum of different compounds (with the wavelength in cm -1 as abscissa).
- the figure 5 presents images of transmission electron microscopy (TEM) and small-angle X-ray scattering curves of compounds (with ordinate intensity and wavelength in nm -1 as abscissa).
- TEM transmission electron microscopy
- small-angle X-ray scattering curves of compounds with ordinate intensity and wavelength in nm -1 as abscissa.
- the process may comprise a step in which zeolite crystals are assembled on the structuring agent. This can thus create a mesoporous material with crystalline zeolite walls.
- the structuring agent creates mesopores during the synthesis of the zeolite.
- the structuring agent is then introduced during the synthesis of the zeolite.
- the invention also relates to the use of reversible micelles for preparing mesoporous materials.
- the micelles may comprise or consist of the compounds described above.
- the subject of the invention is also a mesoporous material obtained according to the method described above.
- the mesoporous material also comprises micropores.
- the presence of intra-crystalline mesopores on zeolite catalysts can improve the accessibility and transport of reagents and products within the zeolite crystal, while the micropores of the zeolite induce selection properties. of favorite shapes.
- the mesoporous material may comprise or consist of silica, titanium oxide, alumina, metal oxides or mixed compounds comprising these various compositions.
- the subject of the invention is the use of a mesoporous material as a molecular sieve or as a catalyst, in particular of chemical reactions, and in particular in the field of petrochemistry.
- the TEM (or TEM) images were obtained on a JEOL 1200 EX II microscope from microtomed samples.
- Example 1A Synthesis of a Structured Material
- a dispersion 1A is obtained. This dispersion 1A is sintered, a solution 1A is recovered on one side and a structured material 1A on the other.
- PEI Polymethacrylic acid
- PEO polyethylene oxide
- a dispersion 1B is obtained. This dispersion 1B is sintered, a solution 1B is recovered on one side and a structured material 1B on the other.
- Example 1B An alternative to the method of Example 1B, made with polyethyleneimine, is to perform the same procedure as in Example 1B but raising the temperature to 80 ° C after pH adjustment. This variant leads to the dispersion 1C, then after filtration and separation of the solid, to the solution 1C and to the structured material 1C.
- Comparative Example 2A Synthesis of a Porous Material by Calcination
- the structured material 1A undergoes calcination according to the following profile to respectively give the mesoporous materials 2A.
- the powders are allowed to come to room temperature and give the mesoporous materials 2A.
- the figure 2 represents the adsorption-desorption isotherms performed to characterize the porous material 2A.
- Comparative Example 2B Synthesis of a Porous Material by Calcination
- the structured material 1B undergoes calcination according to the following profile to respectively give the mesoporous materials 2B.
- the powders are allowed to come to room temperature and give the mesoporous materials 2B.
- the figure 2 represents the adsorption-desorption isotherms performed to characterize the porous material 2B.
- Comparative Example 2C Synthesis of a Porous Material by Calcination
- the structured material 1C undergoes calcination according to the following profile to respectively give the mesoporous materials 2C.
- the powders are allowed to come to room temperature and give the mesoporous materials 2C.
- Example 3A Synthesis of a porous material according to the invention ("ex situ washing")
- a dispersion 1A as described in Example 1A is filtered.
- the powder 1A obtained is dispersed in water (same volume as dispersion 1) at pH 8 for 24 hours, then the dispersion 3A is filtered on sintered material, the mesoporous material 3A is obtained on one side and then dried. at 60 ° C for 12h, and 3A solution (filtrate) is recovered and can be reused.
- Example 3B Synthesis of a porous material according to the invention ("ex situ washing")
- a dispersion 1B as described in Example 1B is filtered.
- the powder 1 obtained is dispersed in water (same volume as dispersion 1) at pH 8, with stirring, for 24 hours, then the dispersion 3B is filtered on sintered material, the mesoporous material 3 is obtained from a side, then dried at 60 ° C for 12h, and the solution 3B (filtrate) is recovered and can be reused.
- the mesoporous material 3B is characterized by its nitrogen adsorption / desorption isotherm on the figure 3 .
- Example 3C Synthesis of a porous material according to the invention ("ex situ washing")
- a dispersion 1C as described in Example 1C is filtered.
- the powder 1C obtained is dispersed in water (same volume as dispersion 1) at pH 8 for 24 hours, then the dispersion 3C is filtered on sintered material, the mesoporous material 3C is obtained on one side and then dried. at 60 ° C for 12h, and the solution 3C (filtrate) is recovered and can be reused.
- the mesoporous material 3C is characterized by its nitrogen adsorption / desorption isotherm on the figure 3 .
- Example 4C Synthesis of a porous material according to the invention ("washing in situ")
- Example 1C To a dispersion 1C as described in Example 1C is added a base (NaOH, 1M) until a pH 8 is obtained. The dispersion is stirred for 24 hours and then filtered. On one side, the filtrate corresponds to the mesoporous material 4C, this dried at 60 ° C for 12h, and on the other hand, the solution 4 (filtrate) is recovered and can be reused.
- a base NaOH, 1M
- the 4C material is characterized by X-ray scattering and transmission electron microscopy. These two analyzes show that the material 4, obtained after washing, has an ordered mesostructure, with a correlation distance of 1.34 nm.
- the figure 4 presents the IR spectra of the porous material 4C obtained by washing in situ the porous material 2C obtained by calcination and the material 1C.
- the large OH peak in the 3500 cm -1 region is probably due to the greater amount of water in washed materials, as suggested by the peak at 1640 cm -1 .
- the highest amount of water may be related to the porosity created by washing at pH 8.
- the peak at 3000 cm -1 decreases in intensity, which tends to show the decrease, or even the disappearance, of organic material in the washed 4C and calcined 2C compounds.
- the material 1C gave after washing in situ the mesoporous material 4C.
- the 4C solution, recovered after filtration and separation of the mesoporous material 4C, is reused as such for a new synthesis of material.
- a synthesis procedure identical to that of the material 1C is therefore performed, from the solution 4C (TEOS addition, pH brought to 2, then to 5, mixture 24h, at room temperature).
- a structured material 5C is then obtained. It is washed at pH 8 and after filtration and separation, the material 6C is obtained.
- the X-ray scattering results presented on the figure 5 show that the material 1C is mesostructured, and that the porous material 4C is also mesostructured. After recycling the polymers, the new formed material 6C also has a structure on the mesoscopic scale. The observed correlation distance is 12.3 nm.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Dispersion Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Claims (6)
- Verfahren zur Herstellung von mesoporösem Material, umfassend die folgenden Schritte:- (a) Herstellen einer wässrigen Lösung mindestens eines strukturierenden Mittels, das mindestens zwei strukturierende Teile aufweist, die von mindestens einem reversiblen nicht-kovalenten Interaktionstyp verbunden sind und eines Vorläufers eines mesoporösen Materials,- (b) Bilden des mesoporösen Materials durch anorganische Polykondensation,- (c) Trennen der mindestens zwei Teile des strukturierenden Mittels bei niedriger Temperatur durch eine gegenüber Schritt (a) inverse Modifizierung eines physikalisch-chemischen Parameters,- Rückgewinnen von mindestens 50 Gew.-% der zwei nicht abgebauten strukturierenden Teile und des mesoporösen Materials,dadurch gekennzeichnet, dass:- die strukturierenden Teile hydrophile, wasserlösliche Polymere sind, ausgewählt als den doppelt hydrophilen Block-Copolymeren, den doppelt hydrophilen Pfropfpolymeren, den Dreiblock-Copolymeren, den Kammpolymeren, den Pfropfpolymeren, den statistischen Copolymeren, den Terpolymeren und den Homopolymeren,- der Vorläufer mesoporösen Materials aus den Vorläufern von Siliziumoxid, Aluminiumoxid, Siliziumoxid-Aluminiumoxid, Zirkon, Titan, Aluminiumalkoxyden, Alkoxyden oder Titan- oder Zirkoniumsalzen ausgewählt ist,- das Gewichtsverhältnis (strukturierender Teil/Gesamtmasse des Vorläufermaterials) von Schritt a) 0,20 bis 0,65 beträgt,- während Schritt a) das strukturierende Mittel mittels Verbindung durch Micellisierung in Wasser der strukturierenden Teile gebildet wird, wobei diese Verbindung durch Modifizierung von mindestens einem physikalisch-chemischen Parameter induziert ist, ausgewählt aus dem pH und der Temperatur.
- Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass das strukturierende Mittel identische strukturierende Teile umfasst.
- Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass das strukturierende Mittel unterschiedliche strukturierende Teile und insbesondere von zwei, drei, vier, ja sogar fünf unterschiedlichen Typen umfasst.
- Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass das strukturierende Mittel in Form von Kolloiden und insbesondere von Kolloiden vorliegt, deren Größe von 10-9 m bis 10-5 m reicht.
- Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass die Temperatur unter oder gleich 200 °C, ja sogar unter oder gleich 100 °C beträgt.
- Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass der Vorläufer mesoporösen Materials das Tetraethylorthosilicat (TEOS) ist.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0708727A FR2926073A1 (fr) | 2007-12-14 | 2007-12-14 | Materiaux mesoporeux et reactifs permettant de les preparer |
FR0709011A FR2926074B1 (fr) | 2007-12-14 | 2007-12-21 | Materiaux mesoporeux et reactifs permettant de les preparer |
PCT/FR2008/052282 WO2009081000A1 (fr) | 2007-12-14 | 2008-12-11 | Materiaux mesoporeux et reactifs permettant de les preparer |
Publications (2)
Publication Number | Publication Date |
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EP2231521A1 EP2231521A1 (de) | 2010-09-29 |
EP2231521B1 true EP2231521B1 (de) | 2018-04-18 |
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ID=39717743
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP08863489.4A Active EP2231521B1 (de) | 2007-12-14 | 2008-12-11 | Verfahren zur herstellung von mesoporösen materialien |
Country Status (6)
Country | Link |
---|---|
US (1) | US8415403B2 (de) |
EP (1) | EP2231521B1 (de) |
DK (1) | DK2231521T3 (de) |
ES (1) | ES2673268T3 (de) |
FR (2) | FR2926073A1 (de) |
WO (1) | WO2009081000A1 (de) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
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FR2989973B1 (fr) | 2012-04-27 | 2014-06-06 | Centre Nat Rech Scient | Materiaux nanostructures biodegradables, leur procede de preparation et leur utilisation pour le transport et le relargage de substances d'interet |
ES2703811T3 (es) * | 2014-07-11 | 2019-03-12 | Total Res & Technology Feluy | Un procedimiento de preparación de materiales cristalinos microporosos mesoporosos que involucra un agente de moldeo de mesoporos recuperable y reciclable |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2004345895A (ja) * | 2003-05-21 | 2004-12-09 | Ajinomoto Co Inc | メソポーラスシリカ及びその製造方法 |
FR2872152B1 (fr) * | 2004-06-24 | 2006-08-11 | Inst Francais Du Petrole | Materiau a porosite hierarchisee comprenant du silicium |
-
2007
- 2007-12-14 FR FR0708727A patent/FR2926073A1/fr active Pending
- 2007-12-21 FR FR0709011A patent/FR2926074B1/fr active Active
-
2008
- 2008-12-11 DK DK08863489.4T patent/DK2231521T3/en active
- 2008-12-11 EP EP08863489.4A patent/EP2231521B1/de active Active
- 2008-12-11 WO PCT/FR2008/052282 patent/WO2009081000A1/fr active Application Filing
- 2008-12-11 US US12/747,797 patent/US8415403B2/en active Active
- 2008-12-11 ES ES08863489.4T patent/ES2673268T3/es active Active
Non-Patent Citations (1)
Title |
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None * |
Also Published As
Publication number | Publication date |
---|---|
FR2926073A1 (fr) | 2009-07-10 |
DK2231521T3 (en) | 2018-07-30 |
WO2009081000A1 (fr) | 2009-07-02 |
US8415403B2 (en) | 2013-04-09 |
US20110028576A1 (en) | 2011-02-03 |
FR2926074A1 (fr) | 2009-07-10 |
FR2926074B1 (fr) | 2010-08-27 |
EP2231521A1 (de) | 2010-09-29 |
ES2673268T3 (es) | 2018-06-21 |
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